1,2,4-oxadiazole derivative, useful as selective herbicide

ABSTRACT

The present invention relates to 1,2,4-oxadiazole derivative of the formula (I) ##STR1## wherein X represents a chlorine or fluorine atom or methyl group, 
     Y represents a chlorine or fluorine atom, 
     n is an integer of 1 or 3. 
     The compounds of the invention have a extremely high selectively between paddy rice or crop plants and weeds, and a strong activity on various weeds. Moreover, the compounds have a very low phytotoxicity to paddy rice and crop plants.

This application is a continuation of Ser. No. 07/373,807, filed Jun.29, 1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel 1,2,4-oxadiazole derivativeshaving an excellent herbicidal activity, methods of preparationtherefore and the herbicidal composition comprising it.

2. Description of the Invention

Phenoxy type herbicides such as 2,4-D, 2,4,5-T, MCPA and MCPB have beenemployed as post-emergence application to control paddy and uplandweeds. Since the phenoxy type herbicides cause the severe phytotoxicityto paddy rice and crop pants depending on the timing of application orthe weather conditions, it has been strongly desired to develop a newtype of herbicide which is able to overcome the phytotoxicity on paddyrice and crop plants and control annual and perennial weeds in paddy andupland field. In other words, a new type of herbicide should have anextremely high selectivity between paddy rice or crop plants and weedsand a strong activity on weeds.

SUMMARY OF THE INVENTION

Under the above circumstances, the present inventors conducted intensivestudies for developing herbicides having low phytotoxicity to paddy riceand crop plants and high selectively between paddy rice or crop plantsand weeds. They found that 1,2,4-oxadiazole derivative of the followingformula(I) has low phytotoxicity, high selectivity and strong activity.

Accordingly, it is an object of the invention to provide a new type ofherbicide which can industrially be produced and which is able tocontrol annual and perennial weed in paddy and upland field with keepinghigh selectivity between crops and weeds.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to 1,2,4-oxadiazole derivative of theformula(I) ##STR2## wherein X represents a chlorine or fluorine atom ormethyl group,

Y represents a chlorine or fluorine atom,

n is an integer of 1 or 3, and

R represents a C₃₋₇ alkyl group; a benzyl group substituted by bromineatom, chlorine atom, fluorine atom, C₁₋₂ alkyl, nitro, amino,acetylamino, thioethoxycarbonylamino, diethylcarbamyl or dimethoxygroup; a phenoxymethyl group substituted by chlorine atom or fluorineatom; a methyl group substituted by bromine atom, chlorine atom,fluorine atom, hydroxy, acetate, haloacetate, C₁₋₂ alkylcarbamate,phenoxybenzoate, methylsulfonate, phenoxyacetate, ethyloxalate, C₁₋₃alkylamino, fluorophenylamino, phthalimide, phenylsulfonylamino,pyrrolidine, thiophenoxy, ethyldithiophosphonate, phenylsulfonyl,diethylthiocarbamate, aminocarbamyl or ethoxycarbonyl group; a phenylgroup substituted by chlorine atom, fluorine atom, methoxy orfluoromethyl group; a C₂₋₃ alkoxy or phenoxy group unsubstituted orsubstituted by chlorine atom, fluorine atom or C₂ alkoxy group; an aminogroup unsubstituted or substituted by C₅ alkyl, acetyl, C₁₋₂alkoxycarbonyl, methylcarbamyl, phenylsulfonyl; a bromine or chlorineatom; a carbonyl group substituted by C₁₋₄ alkylamino, C₁₋₂ alkoxy,amino, azido, halophenylamino, acetylamino, methylsulfonylamino, C₁₋₄alkyl, benzyl or phenyl group; an oxime group substituted by C₁₋₄ alkylor phenyl group; or an imine group substituted by C₁₋₂ alkoxy, amino,hydroxyamino, ethylphosphonyl or chlorine atom.

The compounds of formula(I) of this invention can be prepared, forexample, by the following processes:

(1) Method 1 ##STR3## wherein X represents chlorine atom or methylgroup,

Y represents chlorine atom,

n is an integer of 1 or 3, and

R represents C₃₋₇ alkyl group; a substituted benzyl group; a halomethylgroup; a substituted phenoxymethyl group; a substituted phenyl group; aC₂₋₃ alkoxy or substituted phenoxy group; an ester group; or an estermethyl group.

In other words, the compound(I) of this invention can be prepared byreacting the compound(II) with acylchloride of the compound(III).

The above reaction is carried out at reflux temperature in the presenceof a catalyst for 1 to 5 hours. Various solvents can be used in thisinvention, which include acetone, alcohol, dioxane, etc. For thecatalyst, dimethylamine, trimethylamine, boron trifluoride etherate,sodium methoxide, etc. may be used.

(2) Method 2 ##STR4## wherein, X represents chlorine atom or methylgroup,

Y represents chlorine atom,

n is an integer of 1 or 3,

M represents hydrogen or sodium atom,

Z is nitrogen, oxygen or sulfur atom, and

if Z is a nitrogen atom, R₁ or R₂ is a C₁₋₂ alkyl group, hydrogen atom,a substituted phenyl group, an aryl sulfonyl group or a cyclized acylgroup; and

if Z is oxygen or sulfur atom, R₁ is a phenyl group or a substitutedcarbonyl group.

The above reaction is carried out at reflux temperature in the presenceof base. Various solvents can be used in this reaction, which includeacetone, dioxane, toluene or xylene, tetrahydrofuran, acetonitrile, etc.For the base, they may be employed pyridine, triethylamine, potassiumcarbonate, sodium hydride, etc.

(3) Method 3 ##STR5## wherein X represents chlorine atom or methylgroup,

Y represents chlorine atom,

n is an integer of 1 or 3, and

each of R₁ and R₂, which may be same or different, represents a hydrogenatom, C₁₋₄ alkyl group, an acyl group, a sulfonyl group, anunsubstituted or substituted phenyl group, an amino group or a methoxygroup.

The above reaction is carried out at room temperature in the organicsolvent for 30 minutes to 1 hour. For the solvent, alcohol such asmethanol, ethanol and isopropanol, acetone, acetonitrile,tetrahydrofuran, etc. can be used.

(4) Method 4 ##STR6## wherein X and Y represent chlorine atoms,

R represents C₁₋₄ alkyl group, a benzyl group or phenyl group.

The above reaction is proceeded for 1 to 2 hours at -78° C. in theorganic solvent. For the solvent, tetrahydrofuran, diethyl ether can beused.

(5) Method 5 ##STR7## wherein X and Y represent chlorine atoms,

R represents C₁₋₄ alkyl group or a phenyl group and

R₂ represents a hydrogen atom or C₂₋₃ alkyl group.

The above reaction is carried out at reflux temperature in the presenceof the organic solvent. For the solvent, alcohol such as methanol,ethanol and isopropanol, acetone, acetonitrile, tetrahydrofuran, etc.can be used.

(6) Method 6 ##STR8## wherein, X and Y represent chlorine atoms and

R₁ represents C₁₋₃ alkyl group unsubstituted or substituted by methoxygroup.

The above reaction is carried out at reflux temperature in the presenceof the organic solvent. For the solvent, isopropyl alcohol can be used.

(7) Method 7 ##STR9## wherein, X and Y are chlorine atoms,

Z is a nitrogen or oxygen atom, and

if Z is a nitrogen atom, R₁ or R₂ is a hydrogen atom or C₁₋₂ alkylgroup; and if Z is an oxygen atom, R₁ is C₁₋₃ alkyl group.

The above reaction process is carried out a reflux temperature in thepresence of the organic solvent for 1 hour and subsequently at roomtemperature for 15 hours. For the solvent, alcohol such as methanol,ethanol and propanol can be used in order to prepare carbamate group.However, the reaction should be furthermore carried out for 1 to 4 hoursat reflux temperature in the presence of dioxane as a solvent to prepareurea group.

(8) Method 8 ##STR10## wherein X and Y are chlorine atoms, and

R represents C₁₋₂ alkyl group.

The above reaction process is carried out at room temperature in thepresence of the organic solvent for 3 to 4 hours. For the solvent,alcohol such as methanol or ethanol can be used.

(9) Method 9 ##STR11## wherein X and Y represent chlorine atoms,

R₁ represents C₁₋₂ alkyl group, and

R₂ represents a hydrogen atom or hydroxy group.

The above reaction is carried out at room temperature in the presence ofthe organic solvent for 24 hours. For the solvent, alcohol such asmethanol or ethanol can be used.

After the reaction is completed, the final product can be separatedand/or purified by the conventional methods, if necessary. For instance,the reaction mixture is washed with water, followed by distillation ofthe solvent, and the residue being purified by column chromatography toobtain the compound(I) with a high yield.

Other features of the invention will become apparent in the course ofthe following description of the exemplary embodiments which are givenfor illustration of the invention and are not intended to be limitingthereof.

EXAMPLES Example 13-n-propyl-5[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole. Compound No.1

1.02 g of butylamidoxime, 2.40 g of 2,4-dichlorophenoxyacetyl chlorideand 0.14 g of borontrifluoride etherate were added to 50 ml of toluene.The mixture was heated to reflux for 6 hours. After completion ofreaction, the mixture was washed with 100 ml water and then subjected todistillation of toluene, and the residue was purified by columnchromatography using a mixture of solvent(benzene:ether=4:1) to obtain 1g of the desired compound(yield: 69.7%).

Example 2 3-allyl-5-[(2-chloro-4-fluorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 145

0.71 g of 2-chloro-4-fluorophenol, 0.77 g of3-allyl-5-chloromethyl-1,2,4-oxadiazole and 0.83 of potassium carbonatewere added to 20 ml of acetone. After completion of the reaction, theresulting precipitates were filtered out from the mixture and thenacetone was removed by distillation, and the residue was purified bycolumn chromatography (benzene:hexane=1:1) to obtain 1.05 g of thedesired product(yield: 80.8%).

Example 33-diethylcarbamyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadizaole:Compound No. 99

1.58 g of3-ethoxycarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole and0.73 g of diethylamine were added to 30 ml of methanol. The mixture wasstirred at room temperature for 1 hour. The resulting precipitates werefiltered out from the reaction mixture and then washed with 50 ml ofmethanol. Upon drying the white solid, 1.46 g of the desired product(yield: 84.9%) was obtained.

Example 43-ethylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 112

0.95 g of3-ethoxycarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole wasadded to 30 ml of tetrahydrofuran. The mixture was cooled to -78° C.,and then 3 ml of ethylmagnesium bromide (2M solution) was addeddropwise. After the mixture was stirred at -78° C. for 1 hour, it waspoured into cold aqueous 5% HCl solution. After the resulted product wasextracted with ether and concentrated, it was purified by columnchromatography(hexane:ethylacetate=4:1) to obtain 0.75 g of the desiredproduct(yield: 83.0%).

Example 53-(alpha-hydroxyiminopropyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 119

0.9 g of3-ethylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole and0.21 g of hydroxyamine hydrochloride were added to 10 ml of methanol.The mixture was heated to reflux for 4 hours. After evaporation ofmethanol, water was added to the residue. The aqueous solution wasextracted with ethylacetate. After evaporation of ethylacetate, theresidue was purified by column chromatography(benzene:ether=1.1) toprovide 0.80 g of the desired product(yield: 85.0%).

Example 63-(1-hydroxybutyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 138

0.316 g of3-propylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole and0.20 g of aluminum isopropoxide were added to 10 ml of isopropanol. Themixture was heated to reflux for 48 hours. After evaporation ofisopropanol, water was added to the residue. The aqueous solution wasextracted with ethylacetate. After evaporation of ethylacetate, theresidue was purified by column chromatography(hexane: ethylacetate=3:2)to provide 0.17 g of the desired product(yield: 54.0%).

Example 73-N,N-dimethylureido-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 80

1.57 g of3-azidocarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole wasadded to 20 ml of dioxane. After the mixture was refluxed for 1 hour,0.30 g of dimethylamine was added with formation of bubble and then themixture was stirred at room temperature for 15 hours. The resultingprecipitates were filtered from the mixture and washed with dioxane.Upon drying the precipitates, 0.9 g of the desired product was obtained(yield: 55.0%).

Example 83-(iminomethoxymethyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 125

2.17 g of3-(trichloromethyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole wasadded to 50 ml of methanol. An excess of ammonia gas was added withformation of bubble at 0° C. and then the mixture was stirred at roomtemperature for 4 hours. After evaporation of methanol, water was addedto the residue. The aqueous solution was extracted with ethylacetate.After evaporation of ethylacetate, the residue was purified by columnchromatography(hexane:ethylacetate) to provide 0.92 g of the desiredproduct(yield: 50.9%).

Example 193-iminoaminomethyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole:Compound No. 128

0.62 g of3-iminomethoxymethyl-5-[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazolewas added to 20 ml of methanol. An excess of ammonia gas was added withformation of bubble at 0° C. and then the mixture was stirred at roomtemperature for 24 hours. The resulting white precipitates were filteredfrom the reaction mixture and then washed with methanol. Upon drying thewhite precipitates, 0.54 g of the desired product was obtained(yield:94.4%).

The typical compounds prepared by the similar method to the aboveexamples are shown in Table 1 together with their physical properties.

    TABLE 1      ##STR12##          Element analysis (%)  Compound  Physical Calculated value (Measured     value) No. R n X Y properties C H N NMR (δ, ppm)       1 CH.sub.3 CH.sub.2 CH.sub.2 1 Cl Cl mp 39-40° C. 50.19 4.21     9.75 7.25-6.80(m, 3H), 5.15(s, 2H),       (50.33) (4.28) (9.57) 2.72(5,     2H), 1.92-1.52(m, 2H),          0.98(t, 3H) 2 (CH.sub.3).sub.2 CH 1 Cl     Cl oil 50.19 4.21 9.75 7.20-6.80(m, 3H), 5.20(s, 2H),       (50.08)     (4.18) (9.83) 3.24-2.87(m, 1H), 1.30(d, 6H) 3 (CH.sub.3).sub.3 C 1 Cl Cl     mp 33-34°  C. 51.85 4.69 9.30 7.30-6.80(m, 3H), 5.25(s, 2H),      (51.90) (4.65) (9.22) 1.35(s, 9H) 4 CH.sub.2CHCH.sub.2 1 Cl Cl oil     50.55 3.54 9.82 7.40-6.80(m, 3H), 6.30-5.70       (50.58) (3.49) (9.78)     (m, 1H), 5.35-5.10(m, 4H),          3.65-3.45(m, 2H)      5     ##STR13##      1 Cl Cl mp 40-41°      C. 56.65(56.60) 4.76(4.83) 8.26(8.28) 7.25-6.85(m, 3H), 5.40(m,     1H),5.20(s, 2H), 3.25(s, 2H), 2.10-1.85(m, 4H), 1.75-1.42(m, 4H)  6      ##STR14##      1 Cl Cl oil 54.41(54.25) 3.12(3.18) 7.93(7.80) 7.27-6.65(m, 7H),     5.10(s, 2H),3.90(s, 2H)      7     ##STR15##      1 Cl Cl mp 65-66°      C. 46.41(46.47) 2.68(2.70) 6.76(6.67) 7.30-6.65(m, 7H), 5.02(s,     2H),3.80(s, 2H)      8     ##STR16##      1 Cl Cl mp 75-76°      C. 49.58(49.62) 2.60(2.65) 7.23(7.17) 7.30-6.70(m, 6H), 5.30(s,     2H),4.20(s, 2H)      9     ##STR17##      1 Cl Cl mp 42-43°      C. 58.47(58.42) 4.04(4.09) 8.02(8.11) 7.10-6.80(m, 7H), 5.00(s,     2H),4.10(s, 2H), 2.20(s, 3H)      10     ##STR18##      1 Cl Cl mp 33-34°      C. 59.52(59.60) 4.44(4.51) 7.71(7.59) 7.30-6.70(m, 7H), 5.10(s,     2H),3.95(s, 2H), 2.50(q, 2H),1.18(t, 3H)      11     ##STR19##      1 Cl Cl oil 50.64(50.73) 2.75(2.71) 6.95(6.92) 7.50-6.70(m, 7H),     5.15(s, 2H),4.10(s, 2H)      12     ##STR20##      1 Cl Cl mp 87-88°      C. 53.85(53.78) 3.19(3.22) 7.39(7.43) 7.30-6.70(m, 6H), 5.80(s,     2H),5.25(s, 2H), 3.90(s, 2H)      13     ##STR21##      1 Cl Cl mp 68-69° C. 50.55(50.50) 2.92(2.91) 11.05(11.08)     8.00-6.80(m, 7H), 5.20(s, 2H),4.05(s, 2H)      14     ##STR22##      1 Cl Cl mp 95-95° C. 54.88(54.82) 3.74(3.69) 12.00(12.09)     7.20-6.40(m, 7H), 5.20(s, 2H),4.00(bs, 2H), 3.88(s, 2H)      15     ##STR23##      1 Cl Cl mp 87-88° C. 55.12(55.16) 3.85(3.88) 10.71(10.68)     7.50-6.95(m, 7H), 5.15(s, 2H),4.20(s, 2H), 3.10(bs, 1H),1.95(s, 3H)  16      ##STR24##      1 Cl Cl mp 80-81°      C. 52.06(51.98) 3.91(3.87) 9.59(9.64) 7.50-6.90(m, 7H), 5.20(s,     2H),3.95(s, 2H), 2.98-2.80(m, 3H),1.33(t, 3H)      17     ##STR25##      1 Cl Cl oil 58.07(58.15) 4.87(4.80) 9.67(9.63) 7.30-6.60(m, 7H),     5.20(s, 2H),4.00(s, 2H), 3.35(q, 4H),1.28(t, 6H)      18     ##STR26##      1 Cl Cl oil 49.28(49.38) 2.95(3.01) 8.21(8.09) 7.30-6.60(m, 6H),     5.20(s, 2H),4.20(s, 2H)  19 FCH.sub.2 1 Cl Cl mp 63-64° C. 43.33     2.53 10.11 7.38-6.73(m, 3H), 5.47(d, 2H),       (43.28) (2.58) (10.04)     5.32(s, 2H) 20 ClCH.sub.2 1 Cl Cl mp 65-66°  C. 40.92 2.4) 9.54     7.30-6.80(m, 3H), 5.25(s, 2H),       (40.97) (2.48) (9.47) 4.55(s, 2H)     21 BrCH.sub.2 1 Cl Cl oil 35.51 2.07 8.29 7.45-6.81(m, 3H), 5.32(s, 2H),           (35.45) (2.01) (8.35) 4.42(s, 2H) 22 HOCH.sub.2 1 Cl Cl mp     76-77° C. 43.70 2.91 10.19 7.48-6.79(m, 3H), 5.38(s, 2H),     (43.83) (2.87) (10.24) 4.73(s, 2H), 3.82(bs, 1H)      23     ##STR27##      1 Cl Cl oil 52.04(51.98) 2.98(2.93) 7.59(7.55) 7.32-6.62(m, 7H),     5.38(s, 2H),5.22(s, 2H)      24     ##STR28##      1 Cl Cl mp 78-79°      C. 47.60(47.68) 2.48(2.41) 6.94(6.99) 7.34-6.54(m, 6H), 5.43(s,     2H),5.23(s, 2H)      25     ##STR29##      1 Cl Cl mp 54-55° C. 49.63 (49.55) 2.58(2.63) 7.24(7.21)     7.34-6.56(m, 6H), 5.43(s, 2H),5.22(s, 2H)      26     ##STR30##      1 Cl Cl oil 50.67(50.83) 2.90(2.79) 7.39(7.30) 7.30-6.71(m, 7H),     5.21(s, 2H),5.11(s, 2H)      27     ##STR31##      1 Cl Cl mp 57-59°      C. 47.60(47.42) 2.48(2.57) 6.94(6.99) 7.34-6.71(m, 7H), 5.20(s,     2H),5.12(s, 2H)      28     ##STR32##      1 Cl Cl mp 87-88°      C. 49.82(49.97) 2.85(2.88) 7.27(7.32) 7.32-6.62(m, 7H), 5.44(s,     2H),5.24(s, 2H)      29     ##STR33##      1 Cl Cl oil 46.00(46.19) 3.86(3.81) 10.72(10.79) 7.70-6.30(m, 6H),     5.40(s, 2H), 5.22(s, 2H)      30     ##STR34##      1 Cl Cl mp 52-53°      C. 45.44(45.37) 3.16(3.09) 8.84(8.89) 7.31-6.79(m, 3H), 5.28(s,     2H),5.19(s, 3H), 2.21(s, 3H)      31     ##STR35##      1 Cl Cl mp 61-62° C. 45.10(45.24) 3.76(3.72) 12.14(12.19)     7.31-7.12(m, 3H), 6.38(bs, 1H),5.38(s, 2H), 5.12(s, 2H),3.24(q, 2H),     1.23(t, 3H)      32     ##STR36##      1 Cl Cl oil 53.50(53.37) 2.91(2.94) 8.14(8.11) 8.23-6.89(m, 11H),     5.50(s, 2H),5.48(s, 2H)      33     ##STR37##      1 Cl Cl mp 118-119° C. 45.10(45.25) 3.76(3.79) 12.14(12.09)     7.52-7.23(m, 3H), 5.62(s, 2H),5.15(s, 2H), 2.98(s, 6H)      34     ##STR38##      1 Cl Cl mp 69-70°      C. 37.40(37.48) 2.83(2.86) 7.93(7.88) 7.32-6.75(m, 3H), 5.22(s,     2H),5.20(s, 2H), 3.12(s, 3H)      35     ##STR39##      1 Cl Cl mp 54-55°      C. 40.98(40.83) 2.56(2.57) 7.97(7.92) 7.38-6.75(m, 3H), 5.43(s,     2H),5.42(s, 2H), 4.82(s, 2H)      36     ##STR40##      1 Cl Cl oil 37.33(37.28) 2.07(2.11) 7.26(7.29) 7.32-6.83(m, 3H),     5.98(s, 1H),5.43(s, 2H), 5.12(s, 2H)      37     ##STR41##      1 Cl Cl oil 44.81(44.97) 3.20(3.26) 7.47(7.51) 7.32-6.75(m, 3H),     5.43(s, 2H),5.21(s, 2H), 4.21(q, 2H),1.23(t, 3H)      38     ##STR42##      1 Cl Cl oil 45.25(43.49) 2.51(2.48) 5.86(5.92) 7.64-6.23(m, 6H),     5.31(s, 2H),5.30(s, 2H), 4.78(s, 2H),      39     ##STR43##      1 Cl Cl mp 99-101° C. 41.01(40.88) 3.15(3.08) 11.04(11.10)     7.42-6.81(m, 3H), 6.12(bs, 1H),5.21(s, 2H), 5.20(s, 2H), 3.42(t, 4H)  40     CH.sub.3 NHCH.sub.2 1 Cl Cl mp 133-134° C. 45.85 3.85 14.58     7.30-6.70(m, 3H), 5.20(s, 2H),       (45.98) (3.79) (14.64) 3.85(s, 2H),     2.45(s, 3H),          2.20(bs, 1H) 41 CH.sub.3 CH.sub.2 NHCH.sub.2 1 Cl     Cl oil 47.70 4.34 13.91 7.30-6.70(m, 3H), 5.20(s, 2H),       (47.98)     (4.38) (13.83) 3.85(s, 2H), 2.60(q, 2H),          2.10(bs, 1H), 1.15(t,     3H) 42 (CH.sub.3 CH.sub.2).sub.2 NCH.sub.2 1 Cl Cl oil 50.92 5.19 12.73     7.30-6.70(m, 3H), 5.20(s, 2H),       (50.85) (5.22) (12.78) 3.85(s, 2H),     2.68(q, 4H),          1.05(t, 6H)      43     ##STR44##      1 Cl Cl oil 52.19(52.04) 3.26(3.19) 11.42(11.70) 7.30-6.40(m, 7H),     5.20(s, 2H),4.37(s, 2H), 3.37(bs, 1H),      44     ##STR45##      1 Cl Cl mp 98-99° C. 49.14(49.29) 3.83(3.89) 12.28(12.34)     7.41-6.80(m, 3H), 5.20(s, 2H),4.65(s, 2H), 3.33(t, 2H),2.50-2.05(m, 4H)     45      ##STR46##      1 Cl Cl oil 53.70(53.85) 3.98(3.91) 11.05(11.12) 7.80-6.74(m, 8H),     5.20(s, 2H),4.52(s, 2H), 2.95(s, 3H)      46     ##STR47##      1 Cl Cl oil 46.50(46.54) 3.70(3.78) 8.56 (8.61) 7.62-6.85(m, 7H),     5.21(s, 2H),4.50(s, 2H), 3.36(t, 2H),1.80-1.62(m, 2H), 1.16(t, 3H)  47      ##STR48##      1 Cl Cl oil 52.96(52.89) 3.70(3.74) 10.29(10.33) 7.32-6.85(m, 3H),     6.81(m, 2H),5.23(s, 2H), 4.70(s, 2H),3.18(m, 2H), 2.40(m, 4H)  48      ##STR49##      1 Cl Cl oil 46.69(46.82) 3.30(3.29) 8.59(8.54) 7.85-6.83(m, 7H),     5.81-4.90(m, 5H), 4.52(s, 2H), 3.84(d, 2H)      49     ##STR50##      1 Cl Cl oil 37.93(37.77) 3.87(3.81) 6.32(6.38) 7.50-6.90(m, 3H),     5.35(s, 2H),4.80-4.10(m, 6H), 1.35(t, 6H)      50     ##STR51##      1 Cl Cl oil 52.33(52.18)  3.27(3.20) 7.63(7.77) 7.41-6.72(m, 8H),     5.20(s, 2H),4.08(s, 2H)      51     ##STR52##      1 Cl Cl mp 75-76°      C. 48.13(48.25) 3.01(3.11) 7.02(6.90) 7.87-6.80(m, 8H), 5.31(s,     2H),4.58(s, 2H)      52     ##STR53##      1 Cl Cl oil 46.16(46.33) 4.39(4.40) 10.77(10.79) 7.30-6.85(m, 3H),     5.25(s, 2H),4.15(s, 2H), 3.28(q, 4H),1.05(t, 6H)      53     ##STR54##      1 Cl Cl mp 120-122° C. 41.65(41.53) 3.16(3.10) 17.67(17.80)     7.31-6.90(m, 3H), 5.30-4.91(m, 5H), 4.28(s, 2H)      54     ##STR55##      1 Cl Cl mp 35-36°      C. 47.15(47.22) 3.65(3.73) 8.46(8.39) 7.35-6.95(m, 3H), 5.30(s,     2H),4.15(q, 2H), 3.75(s, 2H), 1.20(t, 3H)      55     ##STR56##      1 Cl Cl mp 100-101° C. 56.10(56.37 3.14(3.12) 8.72(8.83)     8.10-7.80(m, 2H), 7.40-6.90(m, 6H), 5.30(s, 2H)      56     ##STR57##      1 Cl Cl mp 79-80°      C. 50.67(50.78) 2.55(2.52) 7.88(7.81) 7.90-7.70(m, 1H), 7.40-6.90(m,     6H), 5.20(s, 2H)      57     ##STR58##      1 Cl Cl mp 98-99°      C. 48.23(48.47) 2.16(2.18) 7.50(7.54) 7.30-6.90(m, 6H), 5.34(s, 2H)  58      ##STR59##      1 Cl Cl oil 49.38(49.48) 2.33(2.30 7.20(7.17) 8.30-8.10(m, 2H),     7.50-6.90(m, 5H), 5.30(s, 2H)      59     ##STR60##      1 Cl Cl mp 79-81°      C. 53.56(53.69) 3.70(3.73) 7.35(7.31) 7.50-6.70(m, 6H), 5.25(s,     2H),3.80(s, 6H)      60     ##STR61##      1 Cl Cl mp 104-105° C. 52.19(52.28) 2.82(2.79) 14.04(14.01)     8.70-8.50(m, 1H), 8.00-6.80(m, 6H), 5.30(s, 2H)      61     ##STR62##      1 Cl Cl mp 94-95°      C. 47.72(47.88) 2.46(2.43) 8.56(8.52) 7.80-6.80(m, 6H), 5.30(s, 2H)  62      ##STR63##      1 Cl Cl mp 91-92° C. 53.27(53.04) 3.87(3.84) 12.42(12.48)     7.25-7.06(m, 3H), 6.60(d, 1H),5.75(d, 1H), 5.40(s, 2H),3.75(s, 3H),     2.20(s, 3H)      63     ##STR64##      1 Cl Cl mp 120-121° C. 58.81(58.66) 3.49(3.45) 8.07(8.10)     7.60-6.80(m, 10H), 5.30(s, 2H)  64 CH.sub. 3 CH.sub.2 O 1 Cl Cl mp     96-97° C. 45.70 3.49 9.69 7.35-6.80(m, 3H), 5.15(s, 2H),     (45.98) (3.41) (9.74) 4.33(8, 2H), 1.48(t, 3H) 65 CH.sub.3 CH.sub.2     CH.sub.2 O 1 Cl Cl mp 78-79° C. 47.54 3.96 9.24 7.50-7.20(m, 3H),     5.38(s, 2H),       (47.37) (3.91) (9.32) 4.17(t, 2H), 1.90-1.32(m, 2H),             0.58(t, 3H)      66     ##STR65##      1 Cl Cl mp 94-95°      C. 53.44(53.57) 2.99(3.07) 8.31(8.37) 7.40-7.10(m, 8H), 5.35(s, 2H)  67      ##STR66##      1 Cl Cl mp 97-98°      C. 48.48(48.58) 2.44(2.48) 7.54(7.46) 7.40-6.90(m, 7H), 5.25(s, 2H)  68      ##STR67##      1 Cl Cl mp 75-76°      C. 44.37(44.49) 1.99(1.92) 6.90(6.86) 7.42-6.77(m, 6H), 5.23(s, 2H)  69      ##STR68##      1 Cl Cl mp 70-71°      C. 50.73(50.96) 2.55(2.58) 7.89(7.82) 7.50-6.82(m, 7H), 5.21(s, 2H)  70      ##STR69##      1 Cl Cl mp 81-82°      C. 46.25(46.41) 2.07(2.13) 7.19(7.23) 7.40-6.80(m, 6H), 5.19(s, 2H)  71      ##STR70##      1 Cl Cl mp 59-60°      C. 48.28(28.52) 2.16(2.09) 7.51(7.54) 7.42-6.82(m, 6H), 5.31(s, 2H)  72      ##STR71##      1 Cl Cl mp 84-85°      C. 50.72(50.61) 2.54(2.48) 7.89(7.95) 7.40-6.82(m, 7H), 5.20(s, 2H)  73      ##STR72##      1 Cl Cl mp 58-59°      C. 46.23(46.10) 2.05(2.00) 7.19(7.27) 7.40-6.80(m, 6H), 5.21(s, 2H)  74      ##STR73##      1 Cl Cl mp 43-44°      C. 53.00(53.35) 4.00(4.01) 6.18(6.14) 7.40-6.80(m, 7H), 5.25(s,     2H),4.75(q, 1H), 4.25(q, 2H),1.65(d, 3H), 1.30(t, 3H)  75 H.sub.2 N 1 Cl     Cl mp 175-176° C. 41.56 2.71 16.16 7.45-7.05(m, 3H), 5.05(s, 2H),           (71.71) (2.80) (16.27) 2.85(s, 2H)      76     ##STR74##      1 Cl Cl mp 75-76° C. 51.24(54.38) 4.61(4.58) 12.80(12.77)     7.25-6.85(m, 3H), 5.01(s, 2H),3.30(m, 4H), 1.55(m, 6H)      77     ##STR75##      1 Cl Cl mp 118-119° C. 43.73(43.89) 3.01(2.98) 13.90(13.99)     7.45-7.20(m, 3H), 5.25(s, 2H),2.85(bs, 1H), 2.30(s. 3H)      78     ##STR76##      1 Cl Cl mp 90-91° C. 41.53(41.47) 2.85(2.90) 13.21(13.23)     7.65(bs, 1H), 7.60-7.20(m, 3H),5.65(s, 2H), 4.01(s, 3H)      79     ##STR77##      1 Cl Cl mp 136-137° C. 43.39(43.48) 3.34(3.48) 12.65(12.58)     7.30-6.90(m, 4H), 5.30(s, 2H),4.10(q, 2H), 1.25(t, 3H)      80     ##STR78##      1 Cl Cl mp 93-94° C. 43.54(43.31) 3.65(3.69) 16.92(16.90)     9.60(bs, 1H), 7.60-7.20(m, 3H),5.50(s, 2H), 2.90(s, 6H)      81     ##STR79##      1 Cl Cl mp 208-210° C. 41.66(41.42) 3.50(3.41) 17.67(17.81)     7.90(bs, 1H), 7.50-7.10(m, 4H),5.25(s, 2H), 3.22(d, 3H)      82     ##STR80##      1 Cl Cl mp 57-58° C. 41.69(41.93) 2.45(2.44) 14.59(14.56)     8.78(s, 1H), 7.28-6.81(m, 4H),5.19(s, 2H)      83     ##STR81##      1 Cl Cl mp 122-123° C. 46.39(46.57) 3.16(3.21) 10.14(10.19)     8.02-6.83(m, 8H), 5.20(s, 2H),3.42(s, 3H)  84 (CH.sub.3).sub.2 NCHN 1 Cl     Cl oil 45.73 3.84 17.78 8.51(s, 1H), 7.37-6.99(m, 3H),       (15.90)     (3.85) (17.74) 5.14(s, 2H), 3.21(s, 3H)          3.10(s, 3H)  85      ##STR82##      1 Cl Cl mp 70-71° C. 47.29(47.52) 3.97(3,99) 12.73(12.78)     7.31-6.90(m, 3H), 5.12(s, 2H),4.30(q, 2H), 2.21(s, 2H),1.30(t, 3H)  86      ##STR83##      1 Cl Cl mp 65-66° C. 48.85(48.80) 4.39(4.39) 12.21(12.23)     7.30-6.80(m, 3H), 5.12(s. 2H),4.78(q, 2H), 2.53(q, 2H),1.16(m, 6H)  87      ##STR84##      1 Cl Cl mp 161-162° C. 50.41(50.49) 2.91(2.92) 14.70(14.68)     8.68-8.61(d, 1H), 7.45-6.93(m, 7H), 5.10(s, 2H), 4.92(d, 1H)  88      ##STR85##      1 Cl Cl mp 140-141° C. 46.77(46.52) 2.60(2.69) 7.27(7.11)     7.45-6.74(m, 8H), 5.32(s, 2H)  89 Cl 1 Cl Cl mp 58-59° C. 38.67     1.80 15.03 7.40-7.15(m, 3H), 5.45(s, 2H)       (38.50) (1.86) (15.01) 90     Br 1 Cl Cl mp 62-63° C. 44.28 2.05 11.48 7.38-7.15(m, 3H),     5.40(s, 2H)       (44.16) (2.01) (11.39)      91     ##STR86##      1 Cl Cl mp 99-101° C. 43.52(42.61) 3.65(3.69) 16.92(16.87)     8.70(bs, 1H), 7.35-7.15(m, 3H),5.22(s, 2H), 3.35(s, 3H),2.90(d, 3H)  92      ##STR87##      1 Cl Cl mp 74-75° C. 45.23(45.31) 4.09(4.11) 16.23(16.29)     7.40-7.42(m, 3H), 5.25(s, 2H),3.32(s, 3H), 3.02(s, 6H)      93     ##STR88##      1 Cl Cl mp 110-112° C. 43.59(43.40) 2.66(2.59) 9.24(9.37)     7.51-7.20(m, 3H), 5.62(s, 2H),3.89(s. 3H)      94     ##STR89##      1 Cl Cl mp 94-95°      C. 45.45(45.37) 3.18(3.21) 8.83(8.78) 7.30-6.80(m, 3H), 5.30(s,     2H),4.48(q, 2H), 1.45(t, 3H)      95     ##STR90##      1 Cl Cl mp 162-163° C. 43.73(43.85) 3.00(3.01) 13.91(13.88)     8.80(bs, 1H), 7.50-7.20(m, 3H),5.60(s, 2H), 2.88(d, 3H)      96     ##STR91##      1 Cl Cl mp 90- 91° C. 48.85(48.97) 4.36(4.32) 12.21(12.30)     7.30-6.90(m, 3H), 5.40(s, 2H),3.50(t, 2H), 1.70-1.30(m, 5H),1.05(t, 3H)     97      ##STR92##      1 Cl Cl mp 110-111° C. 47.58(47.42) 3.35(3.34) 12.81(12.92)     7.50-7.00(m, 5H), 5.40-5.20(m, 4H), 4.40-4.00(m, 2H)      98     ##STR93##      1 Cl Cl mp 105-106° C. 39.63(36.89) 2.67(2.68) 18.48(17.37)     7.45-7.10(m, 3H), 6.10(bs, 3H)5.50(s. 2H)      99     ##STR94##      1 Cl Cl mp 104-106° C. 48.85(48.77) 4.40(4.38) 12.20(12.25)     7.50-7.10(m, 3H), 5.45(s, 2H),3.55( q, 4H), 1.25(t, 6H)      100     ##STR95##      1 Cl Cl mp 114-115° C. 45.59(45.64) 3.51(3.48) 13.29(13.32)     7.60-7.30(m, 3H), 5.65(s, 2H),3.05(s, 6H)      101     ##STR96##      1 Cl Cl mp 68-70° C. 43.39(43.16) 3.35(3.32) 12.65(12.61)     7.41-6.70(m, 3H), 5.32(s, 2H),3.70(s, 3H), 3.31(s, 3H)      102     ##STR97##      1 Cl Cl mp 116-118° C. 47.29(47.38) 3.97(4.02) 12.73(12.65)     7.60-7.35(m, 3H), 5.65(s, 2H),3.38(q, 2H), 1.90-7.40(m, 2H),0.98(t, 3H)     103      ##STR98##      1 Cl Cl mp 173-175° C. 41.69(41.64) 2.45(2.47) 14.59(14.62)     7.90(bs, 2H), 7.60-7.30(m, 3H),5.65(s, 2H)      104     ##STR99##      1 Cl Cl mp 103-104° C. 38.24(38.47) 1.61(1.58) 22.29(22.35)     7.45-7.15(m, 3H), 5.25(s, 2H)      105     ##STR100##      1 Cl Cl mp 132-133° C. 45.08(45.21) 2.27(2.29) 14.02(14.05)     9.85(bs, 1H), 8.35-8.15(m, 2H),7.90-7.75(m, 1H), 7.55-7.45(m, 1H),7.45-7.     20(m, 2H), 4.90(s, 2H)      106     ##STR101##      1 Cl Cl mp 157-158° C. 52.77(52.88) 3.05(3.03) 11.53(11.49)     10.45(bs, 1H), 7.90-7.05(m, 8H),5.50(s, 2H)      107     ##STR102##      1 Cl Cl mp 142-143° C. 50.28(50.38) 2.64(2.67) 10.99(10.90)     10.5(bs, 1H), 7.90-6.85(m, 7H),5.62(s, 2H)      108     ##STR103##      1 Cl Cl mp 152-153° C. 48.21(48.45) 2.53(2.57) 10.54(10.60)     10.4(bs, 1H), 7.80-7.05(m, 7H),5.45(s, 2H)      109     ##STR104##      1 Cl Cl mp 128-129° C. 43.66 (43.80) 2.75(2.72) 12.72(12.68)     7.39-7.28(m, 3H), 5.60(s, 2H),4.75(bs, 1H), 2.42(s, 3H)      110     ##STR105##      1 Cl Cl mp 175-176° C. 36.09(36.01) 2.48(2.50) 11.47(11.53)     7.97(bs, 1H), 7.48-7.25(m, 3H),5.60(s, 2H), 3.18(s, 3H)      111     ##STR106##      1 Cl Cl mp 118-119° C. 46.02(46.17) 2.81(2.75) 9.76(9.68)     7.32-6.81(m, 3H), 5.27(s, 2H),2.72(s, 3H)      112     ##STR107##      1 Cl Cl mp 115-116° C. 47.86(47.62) 3.35(3.28) 9.30(9.16)     7.30-6.82(m, 3H), 5.31(s, 2H),3.08(q, 2H), 1.16(t, 3H)      113     ##STR108##      1 Cl Cl mp 54-56°      C. 49.54(49.39) 3.84(3.74) 8.89(8.96) 7.31-6.80(m, 3H), 5.30(s,     2H),3.17(t, 2H), 1.90-1.50(m, 2H),1.06(t, 3H)      114     ##STR109##      1 Cl Cl mp 60-62°      C. 51.08(50.91) 4.29(4.20) 8.51(8.42) 7.32-6.80(m, 3H), 5.31(s,     2H),3.06(t, 2H), 1.70-1.22(m, 4H),0.98(t, 3H)      115     ##STR110##      1 Cl Cl mp 112-113° C. 51.08(50.87) 4.29(4.18) 8.51(8.45)     7.28-6.81(m, 3H), 5.29(s, 2H),3.30-2.90(m, 1H), 1.80-1.20(m, 5H),     0.97(t, 3H)      116     ##STR111##      1 Cl Cl mp 94-96°      C. 56.22(56.01) 3.33(3.27) 7.71(7.80) 7.70-6.81(m, 8H), 5.30(s,     2H),3.88(s, 2H)      117     ##STR112##      1 Cl Cl mp 81-82°      C. 55.04(55.21) 2.89(2.80) 8.02(8.17) 8.10-7.22(m, 8H), 5.72(s, 2H)     118      ##STR113##      1 Cl Cl mp 163-164° C. 43.72(43.88) 2.98(2.91) 13.91(13.95)     12.02(s, 1H), 7.23-7.20(m, 3H),5.69(s, 2H), 2.32(s, 3H)      119     ##STR114##      1 Cl Cl mp 126-127° C. 45.58(45.45) 3.48(3.53) 13.30(13.28)     12.02(s, 1H), 7.23-7.18(m, 3H),5.65(s, 2H), 2.75(q, 2H), 1.23(t, 3H)     120      ##STR115##      1 Cl Cl mp 139-140° C. 47.29(47.37) 3.94(3.97) 12.73(12.68)     12.10(s, 1H), 7.23-7.20(m, 3H),5.42(s, 2H), 2.82(t, 2H),1.68(m, 2H),     1.01(t, 3H)      121     ##STR116##      1 Cl Cl mp 110-112° C. 48.85(48.71) 4.36(4.32) 12.21(12.27)     12.23(s, 1H), 7.29-7.25(m, 3H),5.42(s, 2H), 2.81(t, 2H),1.53(m, 4H),     0.98(t, 3H)      122     ##STR117##      1 Cl Cl mp 155-156° C. 52.76(52.57) 3.02(3.05) 11.54(11.50)     12.23(s, 1H), 7.28-7.24(m, 3H),5.62(s, 2H)      123     ##STR118##      1 Cl Cl mp 80-81° C. 48.85(48.60) 4.39(4.45) 12.21(12.15)     7.30-6.82(m, 3H), 5.30(s, 2H),4.15(q, 2H), 1.40-1.02(m, 6H)  124      ##STR119##      1 Cl Cl oil 50.29(50.12) 4.78(4.70) 11.74(11.62) 7.30-6.82(m, 3H),     5.30(s, 2H),4.16(q, 2H), 2.75(t, 2H),1.72-0.82(m, 8H)      125     ##STR120##      1 Cl Cl mp 98-100° C. 43.73(43.60) 3.00(3.07) 13.91(13.80)     8.92(bs, 1H), 7.42-7.19(m, 3H),5.58(s, 2H), 3.80(s, 3H)      126     ##STR121##      1 Cl Cl mp 84-86° C. 45.59(45.74) 3.51(3.48) 15.18 (15.11)     9.15-8.85(bs, 1H), 7.55-7.25(m, 3H), 5.60(s, 2H), 3.75(q, 2H),1.20(t,     3H)      127     ##STR122##      1 Cl Cl mp 138-139° C. 39.63(39.78) 2.67(2.68) 18.48(18.45)     9.70(bs, 1H), 7.50-7.20(m, 3H),5.50(s, 2H), 2.88(bs, 2H)      128     ##STR123##      1 Cl Cl mp 168-169° C. 41.84(41.76) 2.81(2.79) 19.51(19.55)     7.95(bs, 1H), 7.50-7.25(m, 3H),5.65(s, 2H), 3.30(bs, 2H)      129     ##STR124##      1 Cl Cl mp 139-140° C. 42.25(42.39) 1.78(1.80) 16.42(16.46)     8.70(bs, 1H), 7.40-7.15(m, 3H),5.35(s, 2H)      130     ##STR125##      1 Cl Cl mp 97-99° C. 39.26(39.39) 2.40(2.39) 14.26(14.21)     7.50-7.20(m, 3H), 5.65(s, 2H),4.00(s, 3H)      131     ##STR126##      1 Cl Cl mp 103-104° C. 41.11(41.03) 4.15(4.17) 9.58(9.63)     7.50-7.20(m, 3H), 5.65(s, 2H),3.95(q, 4H), 1.28(t, 6H)      132     ##STR127##      1 Cl Cl mp 32-33°      C. 47.86(47.69) 3.35(3.36) 9.30(9.28) 7.34-6.81(m, 3H), 5.25(s,     2H),3.27--2.64(m, 5H)      133     ##STR128##      1 Cl Cl mp 51-52° C. 41.87(41.72) 3.20(3.27) 20.35(20.19)     7.45-6.75(m, 3H), 5.22(s, 2H),4.45-4.01(m, 1H), 3.35(d, 2H),3.10-2.85(m,     3H)      134     ##STR129##      1 Cl Cl mp 43-44°      C. 46.86(46.94) 4.21(4.17) 8.41(8.46) 7.41-6.75(m, 3H), 5.26(s,     2H),4.40-4.00(m, 2H), 3.50-3.28(m, 5H), 3.15-2.85(m, 3H)  135 Cl.sub.3 C     1 Cl Cl mp 100-102° C. 33.14 1.39 7.73 7.30-6.82(m, 3H), 5.28(s,     2H)       (33.29) (1.31) (7.61)      136     ##STR130##      1 Cl Cl mp 43-44°      C. 50.77(50.43) 4.87(4.74) 8.46(8.54) 7.30-6.82(m, 3H), 5.29(s,     2H),3.02(s, 1H), 1.87(t, 2H), 1.72(s, 3H), 1.60-1.28(m, 2H),0.95(t, 3H)     137      ##STR131##      1 Cl Cl oil 47.55(47.70) 3.99(3.93) 9.24(9,17) 7.30-6.81(m, 3H),     5.28(s, 2H),4.76(q, 1H), 3.30(d, 1H),1.61-1.30(m, 2H), 0.97(t, 3H)  138      ##STR132##      1 Cl Cl oil 49.07(48.87) 4.75(4.67) 8.80(8.63) 7.30-6.80(m, 3H),     5.28(s, 2H),4.85(q, 1H), 2.80(d, 1H),1.90-1.22(m, 4H), 0.96(t, 3H)  139      ##STR133##      1 Cl Cl oil 47.55(47.40) 3.99 (4.07) 9.24(9.35) 7.30-6.82(m, 3H),     5.29(s, 2H),3.02(bs, 1H), 1.60(s, 6H)      140     ##STR134##      1 F Cl oil 60.29(60.12) 3.77(3.70) 8.79(8.92) 7.22-6.80(m, 8H), 5.20(s,     2H),4.09(s, 2H)      141     ##STR135##      1 F Cl oil 57.07(7.23) 3.27(3.21) 8.32(8.15) 7.40-6.70(m, 7H), 5.20(s,     2H),4.02(s, 2H)  142 CH.sub.3 CH.sub.2 CH.sub.2 1 F Cl oil 53.24 4.44     10.35 7.20-6.85(m, 7H), 5.26(s, 2H),       (53.02) (4.35) (10.27)     2.66(t, 2H), 2.06-1.38(m. 2H),          0.93(t, 3H)      143     ##STR136##      1 Cl F oil 60.29(60.02) 3.77(3.68) 8.79(8.87) 7.30-6.85(m, 8H), 5.35(s,     2H),4.05(s, 2H)  144 CH.sub.3 CH.sub.2 CH.sub.2 1 Cl F oil 53.24 4.44     10.35 7.20-6.80(m, 7H), 5.20(s, 2H),       (53.10) (4.38) (10.21)     2.65(t, 2H), 2.06-1.35(m, 2H),          0.95(t, 3H) 145 CH.sub.2CHCH.sub.     2 1 Cl F oil 53.64 3.73 10.43 7.23-6.75(m, 3H), 6.34-5.79       (53.49)     (3.70) (10.48) (m, 3H), 5.28(s, 2H), 3.58(d, 2H)      146     ##STR137##      1 Cl F oil 54.41(54.48) 2.83(2.81) 7.93(7.86) 7.32-6.72(m, 7H), 5.21(s,     2H),4.02(s, 2H)      147     ##STR138##      1 Cl F oil 57.07(57.30) 2.97(2.95) 8.32(8.37) 7.32-6.62(m, 7H), 5.23(s,     2H),4.02(s, 2H)  148 CH.sub.3 CH.sub.2 CH.sub.2 1 CH.sub.3 Cl mp     44-45° C. 58.54 5.67 10.50 7.15-6.67(m, 3H), 5.15(s, 2H),     (58.39) (5.65) (10.58) 2.78(t, 2H), 2.24(s, 3H),          2.09-1.56(m,     2H), 1.02(t, 3H) 149 ClCH.sub.2 1 CH.sub.3 Cl mp 30-31° C. 48.37     3.66 10.26 7.32-6.72(m, 3H), 5.29(s, 2H),       (48.18) (3.69) (10.22)     4.76(s, 2H), 2.25(s, 3H)      150     ##STR139##      1 CH.sub.3 Cl oil 52.62(52.75) 4.39(4.43) 9.45(9.40) 7.32-6.72(m, 3H),     5.33(s, 2H),5.32(s, 2H), 2.33(s, 3H),2.31(s, 3H)  151 HOCH.sub.2 1     CH.sub.3 Cl mp 71-72° C. 51.88 4.32 11.00 7.32-6.72(m, 3H),     5.32(s, 2H),       (51.64) (4.35) (11.04) 4.82(s, 2H), 4.28(bs, 1H),          2.32(s, 3H)      152     ##STR140##      1 CH.sub.3 Cl mp 64-65° C. 53.33(53.18) 3.40(3.42) 7.31(7.28)     7.32-6.65(m, 6H), 5.23(s, 2H),5.22(s, 2H), 2.32(s, 3H)  153 CH.sub.3     CH.sub.2 O 1 CH.sub.3 Cl mp 86-87°      C. 53.64 4.88 10.42 7.20-6.80(m, 3H), 5.10(s, 2H),       (53.57) (4.81)     (10.47) 4.33(q, 2H), 2.21(s, 3H),          1.46(t, 3H)      154     ##STR141##      1 CH.sub.3 Cl mp 90-91° C. 52.62(52.47) 4.43(4.42) 9.44(9.49)     7.08-6.45(m, 3H), 4.45(q, 2H),2.10(s, 3H), 1.41(t, 3H)      155     ##STR142##      1 CH.sub.3 Cl mp 129-130°      C. 51.16(51.43) 4.30(4.33) 14.91(14.95) 7.70-7.40(bs, 1H), 7.40-6.70(m,     3H), 5.65(s, 2H), 2.78(d, 3H),2.10(s, 3H)      156     ##STR143##      1 CH.sub.3 Cl mp 87-88° C. 52.79(52.70) 4.78(4.82) 14.20(14.15)     7.40-6.70(m, 3H), 5.65(s, 2H),2.90(s, 6H), 2.10(s, 3H)      157     ##STR144##      1 CH.sub.3 Cl mp 108-109°      C. 55.64(55.49) 5.61(5.59) 12.97(13.00) 7.40-6.70(m, 3H), 5.65(s,     2H),4.03(q, 4H), 2.10(s, 3H),1.20(t, 6H)  158 CH.sub.3 CH.sub.2 CH.sub.2     3 CH.sub.3 Cl mp 31-32° C. 64.12 6.50 9.50 7.10-6.60(m, 3H),     3.96(t, 2H),       (64.28) (6.48) (9.44) 2.99(t, 2H), 2.80-1.62(m, 7H),             0.94(t, 3H) 159 ClCH.sub.2 3 CH.sub.3 Cl oil 51.84 4.65 9.31     7.31-6.62(m, 3H), 4.63(s, 2H),       (51.67) (4.60) (9.36) 4.02(t, 2H),     3.17(t, 2H),          2.42-2.12(m, 5H)      160     ##STR145##      3 CH.sub.3 Cl oil 55.48(55.33) 5.24(5.21) 8.63(8.65) 7.31-6.58(m, 3H),     5.28(s, 2H),3.98(t, 2H), 3.17(t, 2H),2.43-2.02(m, 8H)  161 HOCH.sub.2 3     CH.sub.3 Cl mp 65-66° C. 55.28 4.96 9.91 7.27-6.51(m, 3H),     4.73(s, 2H),       (53.37) (4.95) (9.95) 4.55(bs, 1H), 4.01(t, 2H), 3.12              (t, 2H), 2.67-2.10(m, 5H) 162 CH.sub.3 CH.sub.2 O 3 CH.sub.3 Cl     mp 60-61° C. 56.66 5.76 9.44 7.30-6.78(m, 3H), 4.62-4.10     (56.41) (5.81) (9.47) (m, 4H), 3.25(t, 2H), 2.83-2.41          (m, 5H),     1.71(t, 3H)      163     ##STR146##      3 CH.sub.3 Cl mp 52-54° C. 55.47(55.58) 5.29(5.32) 8.62(8.58)     7.00-6.40(m, 3H), 4.43(q, 2H),3.98(t, 2H), 3.23(t, 2H), 2.60-2.20(m,     2H), 2.20(s, 3H), 1.45(t, 3H)      164     ##STR147##      3 CH.sub.3 Cl mp 98-99° C. 54.28(54.41) 5.22(5.18) 13.56(13.62)     7.55(bs, 1H), 7.00-6.40(m, 3H),3.98(t, 2H), 3.23(t, 2H), 2.78(d, 3H),     2.40(m, 2H), 2.10(s, 3H)      165     ##STR148##      3 CH.sub.3 Cl oil 55.64(55.49) 5.61(5.59) 12.97(13.01) 7.00-6.40(m,     3H), 7.98(t, 2H),3.23(t, 2H), 2.90(s, 6H), 2.60-2.20(m, 2H), 2.10(s, 3H)      166     ##STR149##      3 CH.sub.3 Cl oil 58.03(57.88) 6.32(6.29) 11.94(11.97) 7.00-6.40(m,     3H), 4.15-3.80(m, 6H), 3.23(t, 2H), 2.60-2.20(m, 2H), 2.20(s, 3H),     1.20(t, 6H)  167 CH.sub.3 CH.sub.2 CH.sub.2 3 Cl Cl oil 53.35 5.12 8.89     7.11-6.62(m, 3H), 3.95(t, 2H),       (53.48) (5.09) (8.83) 2.97(t, 2H),     2.70-2.10(m, 4H),          1.90-1.50(m, 2H), 0.98(t, 3H) 168 ClCH.sub.2     3 Cl Cl oil 44.85 3.42 8.71 7.31-6.65(m, 3H), 4.73(s, 2H),       (44.72)     (3.49) (8.73) 4.01(t, 2H), 3.12(t, 2H),          2.67-2.10(m, 2H)  169      ##STR150##      3 Cl Cl oil 48.71(48.87) 4.06(4.03) 8.12(8.16) 7.31-6.65(m, 3H),     5.12(s, 2H),4.08(t, 2H), 3.15(t, 2H),2.51-2.12(m, 5H)  170 HOCH.sub.2 3     Cl Cl mp 74-75° 47.54 3.96 9.24 7.31-6.65(m, 3H), 4.73(s, 2H),        (47.32) (3.94) (9.28) 4.55(bs, 2H), 4.01(t, 2H), 3.12          (t,     2H), 2.67-2.10(m, 2H)      171     ##STR151##      3 Cl Cl oil 50.07(50.21) 3.25(3.22) 6.49(6.45) 7.31-6.62(m, 6H),     5.23(s, 2H),4.02(t, 2H), 3.17(t, 2H), 2.42- 2.12(m, 2H)      172     ##STR152##      3 Cl Cl mp 57-58°      C. 48.71(48.55) 4.09(4.05) 8.11(8.16) 7.00-6.40(m, 3H), 4.43 (q,     2H),3.98(t, 2H), 3.23(t, 2H), 2.60-2.20(m, 2H), 1.45(t, 3H)  173      ##STR153##      3 Cl Cl mp 90-92° C. 47.29(47.48) 3.98(3.92) 12.72(12.61)     7.55(bs, 1H), 7.00-6.40(m, 3H),3.98(t, 2H), 3.23(t, 2H), 2.78(d,3H),     2.60-2.20(m, 2H), 2.10(s, 3H)      174     ##STR154##      3 Cl Cl mp 60-61° C. 48.85(48.99) 4.40(4.38) 12.20(12.09)     7.00-6.40(m, 3H), 3.98(t, 2H),3.23(t, 2H), 2.90(s, 6H),2.60-2.20(m,     2H)

The compounds of the present invention may be used as they are butnormally they are used in the form such as wettable powders, dusts,emulsion concentrates, suspension concentrates, or granules. Theseformulations may be used as they are or may be used after dilution withwater.

When liquid formulations are applied, the solvent such as water,alcohol, ether, acetone, ester, amide or petroleum ether may be used. Asthe solid carrier, an inorganic powder such as magnesium lime, gypsum,calcium carbonate, silica, alumina, zeolite, clay mineral and resinpowder may be used.

The dosage of the present invention to be used as an active ingredientmay be varied depending on the type of formulation, the manner forapplication, the timing and the weather condition. The dosage is usuallyvaried in the range of 0.25 to 4 Kg/ha.

The compounds of the present invention are sufficiently effective evenif they are applied solely. However, their application in combinationwith one or more types of compounds having herbicidal activity makes itpossible not only to reduce the amount of the active ingredient, butalso to attain the enlargement of the herbicidal spectrum or improve theeffects.

The typical examples of herbicides that can be used together with thecompounds of the present invention are mentioned, for examples,amide-type herbicides such as monalide, propanil, solan, diphenamide,fluoridamide, mefluidine, benzamizole, butachlor and alachlor;dinitroaniline-type herbicides such as trifluralin, benfluralin,profluralin, isopropaline, pendimenthalin and ethalfluralin; urea-typeherbicides such as buturon, monolinuron, parafluron, tetrafluron,linuron, sulfodiazol, buthiuron, chlorosulfuron and sulfomethuronmethyl;carbamate-type herbicides such as chlorobufam, barban, diallate,phenmedipham, butylate, triallate, bentiocarb and methylbencarb;diphenylether-type herbicides such as oxyfluorofen, acifluorfornethyl,lactofen, formesafen and fluoronitrofen; and diazine-type herbicidessuch as oxadiazon and immazaqium.

FORMULATION EXAMPLES

Some examples of the formulations are given below.

Formulation 1 Emulsion Concentrate

30 parts of compound No. 1 of the present invention, 60 parts ofm-xylene and 10 parts of surfactant mixture(polyoxyethylene alkyl arylether and sodium alkyl aryl sulfate) were uniformly mixed and stirred toobtain an emulsion concentrate.

Formulation 2 Wettable Powder

10 parts of compound No. 4 of the present invention, 85 parts of whitecarbon and 5 parts of surfactant mixture(polyoxyethylene alkyl arylether sulfate and polyoxyethylene alkyl and aryl ether) were mixed andpulverized to obtain a wettable powder.

Formulation 3 Granule

3 parts of compound No. 100 of the present invention, 60.0 parts ofbentonite, 35 parts of talc, 0.5 parts of sodium dodecyl benzenesulfonate, 0.5 parts of sodium metasilicate and 1.5 parts of sodiumtripolyphosphate were mixed, and after an addition of a proper amount ofwater, kneaded. The mixture was granulated by using an extrusiongranulating machine and dried by a conventional method to obtaingranules.

TEST EXAMPLE Test Example 1 Herbicidal Test Against Paddy Field Weeds

Paddy field soil was filled in 140 cm² plastic pot and irrigated. Paddyrice seedlings (Variety: Dongjin) of 2.5 leaf stage were transplantedand some amounts of paddy field weeds were also sown. On the second dayafter the transplantation, the predetermined amounts of the compounds ofthe present invention were applied in the form of wettable powder.

During the test period, 2 cm in height of water from the surface of thesoil in pot was maintained. Upon twentieth day after the treatment withcompound of the present invention, the herbicidal effects against theweeds and phytotoxicity against paddy rice plants were examined. Theresults are shown in table 2 and herbicide rating system is shown intable 3.

                                      TABLE 2                                     __________________________________________________________________________    4 kg/ha                                                                       Compound                                                                      NO.   ORYSA                                                                              ECHOR                                                                              SCPJU                                                                             BR.s                                                                             ANEKE                                                                              MOOVA                                                                              CYPDI                                                                              CYPSE                                                                              SAGPY                              __________________________________________________________________________     1    70    95         100  100  100                                           2    40   100         100  100  100                                           3    10    50   0      70        10                                           4    30   100  100    100  100  100                                           5    30    90  100    100  100  100                                           6    40   100  100 100               100   20                                 7    20   100   90    100  100  100                                           8     0   100   50    100  100   70                                           9    20   100  100    100  100  100                                          10    30   100  100    100  100  100                                          11    30   100  100    100  100  100                                          12    20   100  100    100  100  100                                          13     0   100  100    100  100  100                                          14     0    80   70    100  100   80                                          15    30   100   90    100   90  100                                          16      0   90  100    100   90  100                                          17    30   100  100    100  100  100                                          18    50   100  100    100  100  100                                          19    80   100  100 100                    100                                20    20   100  100    100  100  100                                          21    10   100  100 100               100  100                                22    60   100  100 100               100  100                                23    10   100  100 100               100  100                                24    10   100  100 100               100  100                                25    10   100  100 100               100  100                                26    10   100  100 100               100  100                                27    10   100  100 100               100  100                                28     0   100  100 100               100   20                                29    20   100  100 100                70  100                                30    80   100  100 100               100  100                                31    40   100  100 100               100  100                                32    30   100   90              100  100   70                                33    30   100  100 100                    100                                34    50   100  100 100                    100                                35    60   100  100 100               100  100                                36    60   100  100 100               100  100                                37    60   100  100 100               100   50                                38    10   100  100 100               100  100                                39    10   100  100 100               100  100                                40    70   100  100    100  100  100                                          41    70   100  100    100  100  100                                          42    50    80  100    100  100  100                                          43    50   100  100 100                    100                                44    50   100  100 100                    100                                45    10   100  100 100               100   70                                46     0    40   70  50                                                       47    20   100  100 100               100  100                                48    10   100  100 100               100  100                                49    10   100  100    100  100   50                                          50    40   100   90 100                     50                                51    20   100   80 100                     20                                52    40   100  100 100               100   90                                53    70   100  100    100  100  100                                          54    40    80  100    100  100  100                                          55     0    50   20    100   90   60                                          56    20    90   90    100  100   80                                          57     0   100   90    100  100  100                                          58    40    70   20     80   70   50                                          59    30    70   70     80   80   80                                          60    20    80  100    100  100  100                                          61    40    80   90    100  100  100                                          62    10    90   90    100  100  100                                          63    20    90  100    100  100  100                                          64    60   100  100    100  100  100                                          65    50   100  100    100  100  100                                          66    40   100  100    100  100  100                                          67    10   100  100    100  100  100                                          68    20   100   90 100                     0                                 69    40   100  100 100               100  100                                70    30   100   90 100               100   80                                71    50   100  100 100               100  100                                72    10   100  100 100               100  100                                73    10   100  100 100               100  100                                74    60   100  100 100               100  100                                75    100  100         100  100  100                                          76    10    90   90    100   90  100                                          77    60   100         100  100  100                                          78    80   100  100    100  100  100                                          79    40   100         100  100  100                                          80    40   100  100 100               100   80                                81    40   100  100 100               100   60                                82    50   100  100 100               100  100                                83    10    60   50  60                50   50                                84    10    80   90 100                60   90                                85    50   100   90 100               100  100                                86    60   100  100 100               100  100                                87    40   100  100 100                90  100                                88     0    50   0   30                0    0                                 89    70   100  100 100               100  100                                90    60   100  100 100               100  100                                91    10   100  100 100               100  100                                92    10   100  100 100               100  100                                93    60   100  100 100               100  100                                94    30   100  100    100  100  100                                          95    50   100  100 100               100   90                                96    40   100         100  100   70                                          97    60   100         100  100  100                                          98    60   100         100  100  100                                          99    20   100  100    100  100   90                                          100   60   100  100    100  100  100                                          101   80   100  100 100               100  100                                102   50   100  100    100  100  100                                          103   60   100  100 100               100  100                                104   60    90         100  100   90                                          105   50   100  100    100  100  100                                          106    0   100   80  80                     0                                 107   20   100  100  80                     30                                108   10   100   70 100                     0                                 109   60   100  100 100               100  100                                110   60   100  100 100                    100                                111   10   100  100 100               100  100                                112   50   100  100 100               100  100                                113   60   100  100 100               100  100                                114   10   100  100 100               100  100                                115   10   100  100 100               100  100                                116   10   100  100 100               100  100                                117   10   100  100 100               100  100                                118   10   100  100 100               100  100                                119   60   100  100 100                    100                                120   60   100  100 100               100  100                                121   10   100  100 100               100  100                                122   10   100  100 100               100  100                                123   30   100  100 100               100   60                                124   50   100  100 100               100   70                                125   70   100   60 100                90  100                                126   70   100  100 100               100  100                                127   60   100  100 100               100  100                                128   60   100  100 100                    100                                129   70   100  100 100                    100                                130   80   100  100 100               100  100                                131   60   100  100 100                    100                                132   50   100  100 100                80   90                                133   40   100   90 100               100   80                                134   50   100  100 100               100   80                                135   30   100  100 100               100  100                                136   10   100  100 100               100  100                                137   10   100  100 100               100  100                                138   10   100  100 100               100  100                                139   10   100  100 100               100  100                                140   40    90   80 100                90   0                                 141   50   100   90 100               100   0                                 142   50   100   80 100               100   0                                 143   70   100  100 100               100   80                                144   70   100  100 100               100   90                                145   70   100  100 100               100  100                                146   60   100  100 100               100   70                                147   60   100  100 100               100   90                                148   10   100  100 100               100  100                                149   10   100  100 100               100  100                                150   80   100  100 100               100  100                                151   10   100  100 100               100  100                                152   10   100  100 100               100  100                                153   50   100  100 100               100  100                                154   90   100  100 100               100  100                                155   10   100  100 100               100  100                                156   10   100  100 100               100  100                                157   10   100  100 100               100  100                                158   20   100  100    100  100  100                                          159    0    20   80  90                90   20                                160   30    70  100 100                70                                     161   40   100  100 100                70  100                                162   40    60  100 100               100   70                                163   60    80  100 100               100  100                                164   10    40  100 100                50   90                                165    0     60 100 100                90  100                                166    0    40   90 100                80   90                                167   30   100  100    100  100  100                                          168   10    60   50  60                50   50                                169   20   100  100 100                50   90                                170    0   100   90 100                0    60                                171   10    80   40 100                0    0                                 172   20    90  100  60               `50   50                                173    0    50   90 100                0    0                                 174    0    80   90 100                0    70                                __________________________________________________________________________     *BR.s: mixture of annual broad leaf weeds such as ANEKE (dayflower), MOOV     (monochoria), ROTIN (toothcup) etc.                                      

    ______________________________________                                        PADDY WEED SPECIES                                                                                        ENGLISH                                           ABRV.  GENUS-SPECIES NAME   NAME                                              ______________________________________                                        ORYSA  Oryza sativa L.      Rice                                              ECHOR  Echinochloa crus-galli                                                                             Barnyardgrass                                            P. BEAUV. var. oryzicola OHWI                                          SCPJU  Scirpus juncoides ROXB.                                                                            Bulrush                                           CYPDI  Cyperus difformis L. Umbrellaplant                                     CYPSE  Cyperus serotinus ROTTB.                                                                           Flat-sedge                                        ANEKE  Aneilema keisak HASSK.                                                                             Dayflower                                         MOOVA  Monochoria vaginalis PRESL.                                                                        Monochoria                                        ROTIN  Rotala indica KOEHE. Toothcup                                          SAGPY  Sagittaria pygmaea MIQ.                                                                            Arrow head                                        ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________    Herbicide Rating System                                                       Rating                                                                             Description                                                              Percent                                                                            of Main                                                                             Crop         Weed                                                  Control                                                                            categories                                                                          Description  Description                                           __________________________________________________________________________     0   No effect                                                                           No crop reduction                                                                          No weed control                                                  or injury                                                          10   Slight                                                                              Slight discoloration                                                                       Very poor weed control                                     effect                                                                              or stunting                                                        20         Some discoloration,                                                                        Poor weed control                                                stunting or stand loss                                             30         Crop injury more                                                                           Poor to deficient weed                                           pronounced but not                                                                         control                                                          lasting                                                            40   Moderate                                                                            Moderate injury, crop                                                                      Deficient weed control                                     effect                                                                              usually recovers                                                   50         Crop injury more                                                                           Deficient to moderate                                      effect                                                                              lasting, recovery                                                                          weed control                                          60         Lasting crop injury                                                                        Moderate weed control                                            no recovery                                                        70   Severe                                                                              Heavy injury and stand                                                                     Control somewhat less                                      effect                                                                              loss         than satisfactory                                     80         Crop nearly destroyed                                                                      Satisfactory to good                                             a few survivors                                                                            weed control                                          90         Only occasional live                                                                       Very good to excellent                                           plants left  control                                               100  Complete                                                                            Complete crop                                                                              Complete weed                                              effect                                                                              destruction  destruction                                           __________________________________________________________________________

We claim:
 1. A 1,2,4-oxadiazole derivative of the formula ##STR155##wherein X represents a chlorine or fluorine atom or methyl group,Yrepresents a chlorine or fluorine atom, n is 1 or 3, and R represents aphenoxy group unsubstituted or substituted by chlorine atom, fluorineatom or C₂ alkoxy group; an amino group unsubstituted or substituted byC₅ alkyl, acetyl, C₁₋₂ alkoxycarbonyl, methylcarbamyl group orphenylsulfonyl group; a bromine atom or chlorine atom; a carbonyl groupsubstituted by C₁₋₄ alkylamino, C₁₋₂ dialkylamino, C₁₋₂ alkoxy, amino,azido, halophenylamino, acetylamino, methylsulfonylamino, C₁₋₄ alkyl,benzyl or phenyl group; an oxime group substituted by C₁₋₄ alkyl orphenyl group; or an imine group substituted by C₁₋₂ alkoxy, amino,hydroxyamino group, ethylphosphonyl group or chlorine atom.
 2. Aherbicidal composition comprising as an active ingredient one or morecompounds of formula (I) as defined in claim 1 and an inorganic carrier.3. A 1,2,4-oxadiazole derivative of the formula (I) according to claim1, wherein X represents a chlorine atom, Y represents a chlorine atom, nis 1, and R represents a carbonyl group substituted by C₁₋₄ alkylamino,C₁₋₂ dialkylamino, C₁₋₂ alkoxy, amino, azido, halophenylamino,acetylamino, methylsulfonylamino, C₁₋₄ alkyl, benzyl or phenyl group; anoxime group substituted by C₁₋₄ alkyl or phenyl group.
 4. A compoundhaving the structural formula of 3-(dimethylamino)carbonyl-5-(2',4'-dichlorophenoxy) methyl-1,2,4-oxadiazole.